A systematic study of polarizability and microscopic third-order optical nonlinearity in thiophene oligomers

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Abstract
A systematic study of the dependence of the band gap, the linear optical susceptibility, the polarizability α, and the second hyperpolarizability γ, on the number of repeat unit is conducted for the thiophene series from monomer to hexamer. The linear optical susceptibilities for oligomers have been determined from the refractive index measurements on vacuum deposited films using the m lines technique. The orientationally averaged polarizabilities 〈α〉 have been measured from refractive index measurements of THF solutions. The orientationally averaged second hyperpolarizabilities 〈γ〉 have been measured by degenerate four-wave mixing studies of THF solutions. The validity of the Lorentz–Lorenz approximation is tested and found to be satisfactory. The experimental values of 〈α〉 and 〈γ〉 for thiophene and 〈α〉 for bithiophene are found to be in qualitative agreement with those obtained by a recent ab initio calculation which used the finite field method and included diffuse polarization functions. The experimentally observed dependence of 〈α〉 and 〈γ〉 on the number N of the thiophene repeat unit is compared with that predicted by a free electron model, PPP methods, and the ab initio calculations. For the case of polarizability, the repeat unit dependence is in good agreement with that predicted by the ab initio calculations but for the case of second hyperpolarizability, the agreement is not as good.